Isodibenzanthrone-azole and process of preparing the same



' 5 dyestuffs. Otherand further important objects I in the form of an azole ring, such as thiazole or mannerto produce the corresponding anthra- Patented July 23, 1935 ISODIBENZANTHRONE-AZOLE AND 'PROCJ ESS F PREPARINGTHE SAME Alexander J Wuertz; Carrollville; and Myron S. Whelen, Milwaukee, Wis.', assignorsto E.-I. 'du Pont de Nemours & Company, Wilmington,

I Bel a-corporation of Delaware N0 Drawing; Application Apr-i129, 193s,

Serial No. 668,623

16 Claims. (Cl.. 260.44)

-This invention relates to azole compounds of thefisodibenzanthrone series. It is an object of this invention; to prepare novel compounds of the i'sodibenzanthrone series Whichjare useful as vat of this invention will appear as the description proceeds. 1 k

The compounds with which this invention deals are characterized by po'ssessing in their structure an isodibenzanthrone nucleus which is substituted by both nitrogen and an element of the sulfur series, for instance, sulfur or selenium. The inorganic elements are very probably present selenazole; With due allowance for partial decomposition of the azole ringjduring the fusion process by which our novel compounds are formed, they probably constitute mixtures of isodibenzanthrone-diazoles and isodibenzanthrone-mono- 'zoles.' f "The products of this invention are navy'blue to dark blue vat dyestuifs, depending on the particular substituent in the carbon atom of the azole ring, as well as on the presence or absence of substituents, such as halogen, in the ,isodiben'za'nthrone nucleus; They are prepared by caustic fusion ofthe Bzl-halogen-benzanthrone' thiazoles and '-se1enazoles described andjclaimed incur 'copending applicationsfof even date, Ser. Nos; 668,620 and 668,621.

understood The Bz1-halogen benZanthrones-thiazoles are prepared by reacting 2,2 diamino-1,1'-dianthraquinonyl-disulfide with an aldehyde in (known quinone 1,2 -thiazole which is then reduced in concentrated sulfuric 'acid' and reacted simul taneously or subsequently with glycerine to form thebenzanthrone compound. The benzanthronethiazoles. so produced may have a'structure corresponding tojone of the following formulae:

135 C. for

(gammy This benz anthrone-thiazole may then, be halogenated by suspending it in water and treating of sodium washed free of impurities with a'dilute solution with a brominating or, chlorinating agent- The Bzl-ha]0gen-benzanthrone-selenazole may be formed in the same manner by starting with a corresponding selenium compound. Y 1 The caustic fusion-may be carried out along 5 analogous lines with the known procedures for fusing Bzl-halogen benzanthrones to isodibenzanthrones., 906,367. The preferred methodinvolvesthe use of alcoholj'as a diluent and employs a temperature between 100 and 170 C. "It is advantageous, however, to adhere to the lowertemperatures, say 120 to' 140 C., in order to minimize .aeccm position of the azole ring. l j l f, Isodibenz'anthrones substituted in thenucleus may beobtained by'fusing correspondinglysube stituted Bzl halogen-benzanthrone-azoles, or the unsubstituted isodibenZanthrone-azoles may be formedfirst and then subjected to' an operation for introducing substituents aswill 'be readily See, for instance, U. S. Patent No.

by those skilled in the art.

Without limiting our invention to any ,particular procedure, the following examples are given to illustrate, our'lspecific mode of operation. .Th'e parts mentioned are by weight. 7 I 25 Example '1 .Fusion of; Bz1-brom-benzanthrone- 3.3 parts'of sodium are dissolved in parts of alcohol, and thereto are added 20 parts of flaked potassium hydroxide. The melt is'heatedto l C. and maintained at this temperature until com pletely fluid. V I throne-1,2-phenyl-thiazole '(Example 6 of co; pending application, 'Ser. No. 668,620) 'arethen added and the reaction mass is heated at about 10 parts of Bzl-brom-benzanone .-hour.- The fusion mass is then diluted with about 1000 parts of warm water, thoroughly; mixed, a'ndthe precipitated "dyestui'f is filtere'd'off as an insoluble leuco body. It is,

hydroxide and. sodium hydrosulfite' Example 2.-Fusion of Bel-chlor-benzanthrone LZ-phenyL-thiazole 7 parts of sodium are dissolved' in 50-parts 01- alcohol, and thereto are added 50 parts of potassium hydroxide.

pletely fluid.

pending application, Ser. No. 668,620)" are-then added and the reaction mass is heated at about 135 C. for one hour. The isodibenzanthronethiazole body so formedis isolated as in Example 1, and appears to' be identical withthe product therein obtained.

Example 3.Chlorination of thiazole substituted isodibenzanthrone 10 parts of phenyl thiazole-isoviolanthrone (prepared according to Example l above) are dissolved-inloO parts of chlor-sulfonic acid; A trace of iodine is addedfan'd then 5 parts of bromineare introduced over a short'period of time. The whole is then stirred -iunti1 evolution of hydrobromic acid has practically ceased. The dyestuir is'isolated' by pouring the chlor-sulfonic aoidlsolutions onto ice, followed byfiltration and washing.- The product so. obtaineddyes cotton in "greenish navy blue shades reasonably fast to water spotting. It corresponds'in bromine content to a dibromocompound.

Example 5.Chlorinwti0m' of phenyl-thiazOleisodibenzanthrone parts of phenyl thiazole-isoviolanthrone are dissolvedin 100 parts of chlor-sulfonicacid; A trace of'iodin'e' is added, and chlorine is then passed in slowly until the evolution of hydrochloric acid has practically ceased. The chlorinated body thus formed is isolated in a manner analogous to that shown in Examples 3 and 4. It dyes cotton from a greenish-blue vat in greenagainst water spotting. Its chlorine content corresponds to a dichloro compound.

If the Bz1-halogen-benzanthrone-phenyl-thiazoles used in Examples 1 and 2 are replaced respectively by equal weights of the corresponding Bzl-halogen-benzanthrone phenyl selenazoles (obtainable according toExamples. 6 and .7 ct copendingapplication 'Ser. NoL- 668, 621)-, a prod-- The melt is heated to 125 C. and maintained at this temperature until com-- 10 parts of Bz1-ch1or-benzan'-'v throne-1,2-phenyl-thiazo1e (Example 7 of 00- uct of very similar properties is obtained, except of course that it is an isodibenzanthrone-selenazole body instead of a thiazole body. When this product is now subjected to halogenation according to any of the Examples 3, 4 and 5, a product is obtained which isagain Substantially identical in'properties with the productiof the respective example, except of course that it contains selenium instead of sulfur.

It will be understood that many variations and modificationsare possible in our preferred mode of operation without departing from the spirit of this invention.

In the claims below it should be understood thatwhere new products, dyestufis, or articles of inanufactureareclaimed, we mean to include these bodies notonly in substance, but also in "whatever state they exist when applied to materials dyed, printed, or pigmented therewith.

We claim:

1. -A vat dyestufi of the isodibenzanthroneazole series, said dyestufi dyeing cotton innavyblueto dark blue shades of superior water fastnessto those of isodibenzanthrone; and said dyestufi be ing obtainable by subjectingto alkali fusiona compound from the class consisting of a Bzl-habogeh-be'nzanthrone-1,2-thiazo1e anda Bz1ha1ogenbenzanthrone-1,2-selenazole the betaposition in the anthraquinone nucleus of the =azole -com pound adjacent the Bz-ring being unsubstituted.

2. A sulfur containing vat dyestuif of the-isodibenzanthrone series, yielding: upon cotton navy blue to' dark blue dyeings of superionwater-fastness than those'of isodibenzanthr'one, said dye stuiT being obtainable by subjecting. to alkali fuq sion 3. Bzl-halogen-benzanthrone-1,2-thiazolethe beta position in the anthraquinone nucleus of the thiazole compound adjacent the Bi-ringbeing unsubstituted.

3. A vat dyestufi comprising chiefly an isodibenzanthrone-alpha, beta; alpha, beta dithiazole.

41A vatdy'estu'ifcomprised chiefly ofisodi benzanthrone-C 'C diphenyl-alpha, beta;.-alpha", beta" dithiazole.

' 5. The process of producing a vat dyestu'fi of the isodib'enzanthrone series, .whichcomprises subjectingto alkali fusion a Bz'l-halogen-benzan throne-azole of the series consisting of Bz'l-halogen-benz'anthrbne-alpha, beta thiazoles B21 halogen-benzanthrone-alpha, beta 'selenazoles the beta positionin the anthraquinone-nucleus of 'said azole compounds adjacent the Ba-ring being unsubstituted.

6.""I'he process of producing a vat dyestufi of the isodib'en'zanthr'orieseries which comprises subjecting to alkali fusion at Bz'1-ha1ogembenzanthrone-alpha,ibeta thia'zol'e' the beta position in the 'anthraquin'one nucleusof the said thia'zole adjacent the "Bz-ring .be'ing unsubstituted.

7. The process or producing a vat dyestufi'of the isodibenzanthrone series which comprises subjecting to alkali fusion a Bzl-halogen-benzanthronem-phenyl-alpha, beta thiazole the beta position in the 'anthraquinone nucleusof the said 'thiazol'e'adjacent the B'z-ring being unsubstitutedi ish navy blue shades, which are reasonably fast 8 The process of producing a vat dyestuff ofi the isddibe'nzanthrorie. series; which comprises fusing Bzl-halogen-benzanthrone-1,2-C-phenylthiazole with alcoholic caustic alkali at a temperature between 120 and 140 C.

10. The process of producing a vat dyestufi of the isodibenzanthrone series which comprises fusing Bzl-halogen-benzanthrone-1,2-C-phenylthiazole with alcoholic caustic alkali at a temperature between 120 and 140 C., and subjecting the product to halogenation.

11. The process of producing a vat dyestufi of the isodibenzanthrone series which comprises chlorinating an isodibenzanthrone-C-phenyl-alpha, beta thiazole in an inert organic suspending medium.

12. The process of producing a vat dyestufi of the isodibenzanthrone series which comprises chlorinating an isodibenzanthrone-C-phenyl-alpha, beta thiazole in chlorosulfonic acid.

13. The process of producing a. vat dyestufi of the isodibenzanthrone series which comprises brominating an isodibenzanthrone-C-phenyl-alpha, beta thiazole in chlorosulfonic acid.

14. Halogenated isodibenzanthrone-C-pheny1- alpha, beta-thiazoles.

-15. Dichlorinated isodibenzanthrone-C-phenylalpha, beta-thiazoles.

16. Dibrominated isodibenzanthrone-C-pheny1-alpha,beta-thiazoles. v

- ALEXANDER J. WUERTZ.

MYRON S. WHELEN. 

